Catalyst compositions and process for oxychlorination

ABSTRACT

Oxychlorination catalyst compositions which include a catalytically effective amount of an oxychlorination catalyst and a diluent having certain chemical composition and/or physical properties are disclosed. Processes using such oxychlorination catalyst compositions are also described. Some oxychlorination catalyst compositions and processes disclosed herein can increase the optimal operating temperature, and thereby increase the production capacity of an existing reactor, such as a fluid-bed reactor, compared to other oxychlorination catalyst compositions.

PRIOR RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationSer. No. 60/736,524, filed Nov. 14, 2005, which is incorporated hereinby reference in its entirety.

FEDERALLY SPONSORED RESEARCH STATEMENT

Not applicable.

REFERENCE TO MICROFICHE APPENDIX

Not applicable.

FIELD OF THE INVENTION

The invention relates to oxychlorination catalyst compositions forcatalytically oxychlorinating hydrocarbons to chlorinated hydrocarbons,especially compositions comprising an oxychlorination catalyst and adiluent and their applications in oxychlorination processes.

BACKGROUND OF THE INVENTION

Oxychlorination catalyst compositions for the production of chlorinatedhydrocarbons by oxychlorination have been well established for manyyears. Oxychlorination is the reaction of a hydrocarbon, such asethylene or propylene, with hydrogen chloride and oxygen to form waterand the corresponding chlorinated hydrocarbons, such as1,2-dichloroethane (EDC) or 1,2-dichloropropane, preferably in thepresence of an oxychlorination catalyst. The oxychlorination reactionhas been applied worldwide in large industrial scale. For example, theconversion of ethylene to EDC by oxychlorination alone is currently in ascale of million's of tons per year.

One particular method of oxychlorination is the vapor phase reaction ofa hydrocarbon, such as ethylene or propylene, with a mixture of hydrogenchloride (HCl) and a source of oxygen (such as high purity oxygenobtained from an air separation plant where pressure swing absorption orcryogenic separation is employed to remove inert materials, or a diluteoxygen stream such as air or a mixture of oxygen and at least an inertgas) within a fluidized catalyst bed comprising an oxychlorinationcatalyst. A typical oxychlorination catalyst can comprise a metal saltsuch as copper chloride and optionally at least a salt of alkali metals,alkaline metals or rare earth metals deposited on or combined with asupport material or inert carrier, such as particles of silica, alumina,kieselguhr, fuller's earth, clays and alumina silicates or aluminumsilicates or aluminium silicates. For use in fluid-bed catalysis, thesupport material should be readily fluidizable having the properparticle density, resistance to attrition, and particle sizedistribution to be useful in the process without generating excessivecatalyst loss from the reaction zone. Optionally, the catalystcomposition may comprise a diluent which comprises catalytically andchemically inert particles such as alumina and silica having a lowsurface area.

In the oxychlorination of a hydrocarbon (e.g., ethylene), it isdesirable for the oxychlorination catalyst composition to effect a highyield of the desired chlorinated product (e.g., EDC) and a small amountof by-products such as carbon dioxide, carbon monoxide and otherchlorinated materials. In the high volume business of manufacturing EDC,a small increase in the efficiency of ethylene conversion to EDC canprovide significant cost savings. Furthermore, an increase in ethyleneefficiency or selectivity of ethylene to EDC can reduce the amount ofby-products produced, the associated costs to dispose of them properly,and the potential risks to the environment. Selectivity of ethylene toEDC (i.e., ethylene selectivity) is the number of moles of pure EDCproduced per 100 moles of ethylene consumed or converted (i.e., ethyleneconversion) to EDC plus any by-products, whereas ethylene efficiency isdefined as the product of ethylene selectivity times ethyleneconversion. Similarly, selectivity of HCl to EDC (i.e., HCl selectivity)is the number of moles of pure EDC produced per 200 moles of HClconsumed or converted (i.e., HCl conversion) to EDC plus anyby-products, whereas HCl efficiency is defined as the product of HClselectivity times HCl conversion. Similarly, selectivity of oxygen toEDC (i.e., oxygen selectivity) is the number of moles of pure EDCproduced per 50 moles of oxygen consumed or converted (i.e., oxygenconversion) to EDC plus any by-products, whereas oxygen efficiency isdefined as the product of oxygen selectivity times oxygen conversion.

It is also desirable, for economic and environmental reasons, for theoxychlorination catalyst composition to effect a high conversion of HClused in the reaction. Unconverted HCl needs to be neutralized by a baseand the resulting salt must be disposed. Also, high levels ofunconverted HCl in the process generally leads to high HCl “breakthrough” downstream in the reactor which can cause corrosion problems.Hence, it is desirable to operate a reactor at an optimal temperature toprovide high HCl conversion. In commercial applications, a combinationof high HCl conversion and high ethylene efficiency or selectivity ofethylene to EDC is most desirable.

Further, it is desirable to increase the optimal operating temperatureof the oxychlorination catalyst without sacrificing catalyst performancebecause it would be the most cost efficient way to increase theproduction capacity of an existing oxychlorination reactor. In general,an increase in the operating temperatures increases the temperaturedifference between the fluidized catalyst bed and the steam drum, whichis utilized for removing the heat of reaction and maintaining thecontrolled temperature. Therefore, increasing the operating temperaturecan increase the driving force for heat removal and allow for increasedreactor productivity. The optimal operating temperature for the catalystin reactors where the majority of the vent gas is recycled back to thereactor is the point where the HCl conversion and the ethyleneselectivity are optimized. For air-based, once-through reactors, theoptimal operating temperature is the point where the HCl conversion andthe ethylene efficiency are optimized. For example, for a reactorlimited by a steam drum pressure of 211 psig (i.e., 1455 kPa) and/or200° C., an increase in the optimal operating temperature of theoxychlorination catalyst composition from 230° C. to 240° C. wouldresult in an increase of 33% in the production capacity of that reactor.Therefore, there is always a need for oxychlorination catalystcompositions that can run at higher optimal operating temperatures thusproviding an effective way to increase the production capacity of anexisting oxychlorination reactor.

SUMMARY OF THE INVENTION

Disclosed herein are oxychlorination catalyst compositions that canincrease the optimal operating temperature of oxychlorination processeswithout sacrificing catalyst performance.

In one aspect, the oxychlorination catalyst compositions comprise acatalytically effective amount of an oxychlorination catalyst and adiluent comprising particles of an alumina silicate.

In another aspect, the oxychlorination catalyst compositions comprise:

(a) a catalytically effective amount of an oxychlorination catalysthaving a surface area greater than 25 m²/g where the oxychlorinationcatalyst comprises a support material having distributed thereon anactive salt composition; and

(b) a diluent having a surface area between about 0.1 m²/g and about 25m²/g, wherein the support material and the diluent are differentchemically and the average particle size of the catalyst and the diluentis between about 5 and about 300 microns.

Disclosed herein are also oxychlorination processes using theoxychloriation catalyst compositions to increase the optimal operatingtemperature of the oxychlorination processes without sacrificingcatalyst performance.

In one aspect, the oxychlorination processes comprise the step ofcontacting reactants including the hydrocarbon, a source of chlorine,and an oxygen source with an oxychlorination catalyst composition underprocess conditions to prepare a chlorinated hydrocarbon. In someembodiments, the oxychlorination catalyst composition comprises acatalytically effective amount of an oxychlorination catalyst and adiluent comprising particles of an alumina silicate. In otherembodiments, the oxychlorination catalyst composition comprises (a) acatalytically effective amount of an oxychlorination catalyst having asurface area greater than 25 m²/g where the oxychlorination catalystcomprises a support material having distributed thereon an active saltcomposition; and (b) a diluent having a surface area between about 0.1m²/g and about 25 m²/g, wherein the support material and the diluent aredifferent chemically and the average particle size of the catalyst andthe diluent is between about 5 and about 300 microns.

In another aspect, the oxychlorination processes comprise the step ofcontacting reactants including the hydrocarbon, a source of chlorine,and an oxygen source with an oxychlorination catalyst compositioncomprising a catalytically effective amount of an oxychlorinationcatalyst and an inert diluent under process conditions to prepare achlorinated hydrocarbon, wherein the process is run at T_(opt(2)), theoptimal operating temperature of the process, which is at least about 1°C. higher than T_(opt(l)), the optimal operating temperature of aprocess using the same reactor, reactants, production rates andoxychlorination catalyst but without the inert diluent. In someembodiments, the oxychlorination processes are operated at the mosteconomical process conditions.

DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts the EDC selectivity as a function of temperature andcatalyst composition of Examples 1-5 disclosed herein.

FIG. 2 depicts the HCl conversion as a function of temperature andcatalyst composition of Examples 1-5 disclosed herein.

FIG. 3 depicts the carbon oxide selectivity as a function of reactiontemperature and catalyst composition of Examples 1-5 disclosed herein.

FIG. 4 depicts the 1,1,2-trichlororethane selectivity as a function ofreaction temperature and catalyst composition of Examples 1-5 disclosedherein.

FIG. 5 depicts the EDC selectivity as function of temperature andcatalyst composition of Examples 6-9 disclosed herein.

FIG. 6 depicts the HCl conversion as a function of temperature andcatalyst composition of Examples 6-9 disclosed herein.

FIG. 7 depicts the carbon oxide selectivity as a function of reactiontemperature and catalyst composition of Examples 6-9 disclosed herein.

FIG. 8 depicts the 1,1,2-trichloroethane selectivity as a function ofreaction temperature and catalyst composition of Examples 6-9 disclosedherein.

DETAILED DESCRIPTION OF THE INVENTION

In the following description, all numbers disclosed herein areapproximate values, regardless whether the word “about” or “approximate”is used in connection therewith. They may vary by 1 percent, 2 percent,5 percent, or, sometimes, 10 to 20 percent. Whenever a numerical rangewith a lower limit, R^(L) and an upper limit, R^(U), is disclosed, anynumber falling within the range is specifically disclosed. Inparticular, the following numbers within the range are specificallydisclosed: R=R^(L)+k(R^(U)−R^(L)), wherein k is a variable ranging from1 percent to 100 percent with a 1 percent increment, i.e., k is 1percent, 2 percent, 3 percent, 4 percent, 5 percent, . . . , 50 percent,51 percent, 52 percent, . . . , 95 percent, 96 percent, 97 percent, 98percent, 99 percent, or 100 percent. Moreover, any numerical rangedefined by two R numbers as defined in the above is also specificallydisclosed.

This invention provides an oxychlorination catalyst compositioncomprising a catalytically effective amount of an oxychlorinationcatalyst and a diluent such as alumina silicates (also known as aluminumsilicates or aluminium silicates), glass beads, silica, ballotini,alumina, graphite, and silicon carbide. The oxychlorination catalystcomposition can provide a higher optimal operating temperature withoutsacrificing the performance benefits inherent to the undilutedoxychlorination catalyst such as high EDC selectivity, high productpurity, high HCl conversion, and excellent fluidity. As used herein, theterm “catalytically effective amount” is intended to mean any amountthat is effective in generating an EDC production capacity increase ofthe oxychlorination reactor by at least 1%, preferably by at least 10%,more preferably by at least 30%, and most preferably by at least 50%.

In some embodiments, the oxychlorination catalyst composition comprisesfrom about 10 to about 90 percent by weight of the oxychlorinationcatalyst and from about 90 to about 10 percent by weight of the diluent.In other embodiments, the oxychloriation catalyst composition comprisesfrom about 20 to about 80 percent by weight of the oxychlorinationcatalyst and from about 80 to about 20 percent by weight of the diluent.In further embodiments, the oxychlorination catalyst compositioncomprises from about 30 to about 70 percent by weight of theoxychlorination catalyst and from about 70 to about 30 percent by weightof the diluent. In particular embodiments, the oxychlorination catalystcomposition comprises from about 60 to about 40 percent by weight of theoxychlorination catalyst and from about 60 to about 40 percent by weightof the diluent.

Some oxychlorination catalyst compositions described herein can becharacterized by an ethylene to EDC selectivity of at least 96% at atemperature of 230° C. Other oxychlorination catalyst compositions canbe characterized by an ethylene to EDC selectivity of at least 97% at atemperature of 240° C. Some oxychlorination catalyst compositions can becharacterized by substantially the same or higher ethylene to EDCselectivity, HCl conversion and/or higher operating temperatures than acomparable oxychlorination catalyst without a diluent having a surfacearea of less than 25 m²/g.

The oxychlorination catalyst can be any oxychlorination catalyst knownto one of ordinary skill in the art. It can also be prepared by anymethod known to one of ordinary skill in the art. The oxychlorinationcatalyst can contain an active salt composition comprising a copper saltsuch as copper chloride distributed, coated, deposited or supported on asupport material. The active salt composition may also contain an activemetal oxide or metal salt that is co-precipitated with the support.Alternatively, the active salt composition can be unsupported, but fusedinto a molten salt. In some embodiments, the active salt compositionfurther comprises at least one metal salt or oxide derived from a metalselected from the group consisting of alkali metals, alkaline metals(i.e., Group IIA), rare earth metals and combinations thereof. The anionof the metal salt can be any anion known in the art such as chloride,bromide, iodide, nitrate, bicarbonate, carbonate and carboxylates (e.g.,formate and acetate). In some embodiments, the active salt compositioncomprises a copper salt, at least one alkali metal salt, at least onerare earth metal salt, and at least one alkaline metal salt. In otherembodiments, the active salt composition does not contain an alkalimetal salt, an alkaline metal salt, a rare earth metal salt, or atransition metal salt other than a copper salt. Some non-limitingexamples of suitable oxychlorination catalysts, active salt compositionsand support materials are disclosed in PCT Patent Application No. WO81/01284, U.S. Pat. Nos. 3,488,398; 4,339,620; 4,446,249; 4,740,642;4,849,393; 5,292,703; 5,382,726; 5,600,043; 6,872,684; 6,803,342;6,777,373; 6,759,365; and 6,174,834, and Japanese Patent Publication No.11-090233, all of which are incorporated herein by reference in theirentirety.

The average particle size and the particle size distribution of theoxychlorination catalyst, the support material, or the diluent can bemeasured with a particle size analyzer. As used or claimed herein, theaverage particle size and the particle size distribution data are orshould be measured by ASTM D4460-00, which is incorporated herein byreference or by the procedure described below. The average particle sizeand the particle size distribution can be measured with a HoneywellMicrotrac X-100 laser particle analyzer using water as the dispersant.The samples for the measurement can be prepared by adding about 5 ml ofthe particles to 10 ml of a surfactant solution (which is prepared from4 ml of TRITON™ CF-10 (from Rohm and Haas Company, Philadelphia, Pa.)and 6 ml of TRITON™ X-100 (from Rohm and Haas Company, Philadelphia, Pa)diluted with water to 1000 ml) in a 50 ml beaker. The mixture is stirredto wet all particles for about 10 to 15 seconds to generate a slurrythat is then added to the circulator basin of the Microtrac X-100containing about 2 liters of water. Once the proper concentration levelis confirmed by the software (about 10 to 20 seconds), the run isinitiated. The water temperature is held between about 80 and 90° F. TheMicrotrac X-100 particle size analyzer utilizes the laser diffractionmethod to measure the percent of particles in the range of 0.04 to 700microns. The average particle size is the 50% point (by volume) of thesample. The particle size distribution is reported as percentages ofparticles less than some particular size in microns. Alternatively, theaverage particle size and the particle size distribution of the samplescan be measured by an equivalent instrument or method that producesessentially the same results obtained by the Honeywell Microtrac X-100laser particle analyzer.

A person of ordinary skill in the art can recognize that themeasurements of the average particle size and the particle sizedistribution may be subject to errors and/or variations, depending onmany factors such as the type of the particle analyzer used for themeasurement, the calculation method including error correctionalgorithm, the sample preparation method, the amount and nature of thedispersant, the amount and nature of the surfactant and the like. Forthe oxychlorination catalyst compositions disclosed herein, the relativevalues of the average particle sizes and the particle size distributionsof the oxychlorination catalyst, the support material and the diluentare as significant as their absolute values. The relative values of theaverage particle sizes and the particle size distributions of theoxychlorination catalyst, the support material and the diluent can bemeasured by any particle size measurement method known to a skilledartisan. For example, the relative average particle size of the diluentor the support material to the average particle size of theoxychlorination catalyst can be obtained by ASTM D4460-00 or the methoddescribed above or any similar method known to a person skilled in theart.

The surface area of the support material, the oxychlorination catalystor the diluent can be determined by the BET (Bnmauer-Emmet-Teller)method of measuring surface area, as described by S. Brunauer, P. H.Emmett, and E. Teller, Journal of the American Chemical Society, 60, 309(1938), which is incorporated herein by reference. As used or claimedherein, the surface area data are or should be calculated from thenitrogen adsorption isotherm data at 77° K utilizing the BET method. Thesupport material, the oxychlorination catalyst or the diluent can haveeither a high surface area or a low surface area. As used herein, theterm “high surface area” or “high-surface-area” means a surface areagreater than 25 m²/g, preferably greater than about 50 m²/g, morepreferably greater than about 70 m²/g. Further, as used herein, the term“low surface area” or “low-surface-area” means a surface area less than25 m²/g, preferably less than about 20 m²/g, more preferably less thanabout 16 m²/g.

Any support material which is known in the art suitable as a support foroxychlorination catalyst can be used in this invention. Non-limitingexamples of suitable support materials include alumina such as activatedalumina and microgel alumina, silica, magnesia, kieselguhr, fuller'searth, clays, alumina silicates, porous rare earth halides andoxylalides, and combinations thereof. The support material can have asurface area between about 5 m²/g and about 450 m²/g, as determined bythe BET method. In some embodiments, the surface area of the supportmaterial is between about 25 m /g and about 300 m²/g. In furtherembodiments, the surface area of the support material is between about70 m²/g and about 200 m²/g. In certain embodiments, the surface area ofthe support material is between about 70 m²/g and about 240 m²/g.

The support material can have an average particle size ranging fromabout 5 to about 300 microns, from about 20 to about 250 microns, fromabout 20 to about 200 microns, from about 20 to about 150 microns, fromabout 20 to about 120 microns, from about 30 to about 100 microns, orfrom about 30 to about 90 microns. The compacted or tamped bulk densityof the support material can vary between about 0.6 and about 1.6 g/cc,between about 0.7 and about 1.5 g/cc, between about 0.7 and about 1.3g/cc, or between about 0.8 and about 1.3 g/cc.

In fluid-bed oxychlorination catalysis, it is desirable that the supportmaterials have a high surface area because high-surface-area supportmaterials can reduce the tendancy for stickiness of the oxychlorinationcatalyst as the active salt composition is dispersed over a large area.Catalyst stickiness is defined as catalyst particle agglomeration viacopper chloride mobility and bridging from particle to particle underprocess operating conditions. In fixed-bed catalysis, the supportmaterial can have either a high surface area or a low surface area. Thepreferred catalytic process is fluid-bed catalysis using ahigh-surface-area support material.

The oxychlorination catalyst used for the fluid-bed catalysis processcan comprise an active salt or oxide composition uniformly distributed,deposited, coated, co-precipitated with, or supported on ahigh-surface-area support material. The support material can be in theform of particles having proper particle sizes, surface area, porosity,density, resistance to attrition and other characteristics (a) toprovide uniform fluidization, good heat transfer, and minimaltemperature gradients in the reactor bed; (b) to permit adequate contactbetween the active salt composition and the gaseous reactants as theypass through the bed; and (c) to minimize loss of catalyst throughpassage of fine particles from the reactor with the effluent gases.

In some embodiments, the support material having a surface area greaterthan 50 m²/g and the support material is selected from the groupconsisting of alumina silicate, silica, alumina, and combinationsthereof. In a particular embodiment, the support materials are aluminashaving a surface area in the range of about 25 to 250 m²/g, a compactedbulk density in the range of 0.7 to 1.1 g/cc, and an average particlesize ranging from about 5 to about 300 microns. Such alumina supportmaterials are readily fluidizable, relatively stable, mechanicallystrong and resistant to attrition. In some embodiments, the supportmaterial is an alumina having a surface area in the range of about 120to 240 m²/g and an average particle size ranging from about 30 to about90 microns.

It is recognized that some alumina support materials may contain, inaddition to aluminum oxide (Al₂O₃), small amounts of other metalcompounds such as metal oxides. Non-limiting examples of metal oxides inaluminum oxide include sodium oxide, magnesium oxide, titanium oxide andthe like. These alumina support materials are readily useable in thisinvention. Similarly, some alumina silicate support materials maycontain in addition to alumina silicate small amounts of other metalcompounds such as metal silicates and metal oxides. Non-limitingexamples of metal oxides in alumina silicate include sodium oxide,magnesium oxide, iron oxide, and the like. These alumina silicatesupport materials are also readily useable in this invention. The othermetal compounds may occur naturally or be added as separate compounds.

In some embodiments, the active salt composition comprises a coppersalt. The copper salt can be used in the form of a water soluble salt,preferably copper chloride. However, copper oxides or other coppersalts, such as the nitrate salt, carbonate salt and other halide saltslike the bromide salt, that could convert to the chloride during theoxychlorination process can also be used. The amounts of copper salt andother salts in the oxychlorination catalyst depend on the activitydesired and the specific fluidization characteristics of the supportmaterial for fluid-bed catalyst applications. The amount of copper metalcontent can be in the range from about 1% by weight to about 15% byweight, based on the total weight of the oxychlorination catalyst. Insome embodiments, the amount of copper metal content is about 2% byweight to about 8% by weight, based on the total weight of theoxychlorination catalyst. In other embodiments, the amount of coppermetal in the copper salt is in the range from about 3% to about 6% byweight based on the total weight of the oxychlorination catalyst. Inother embodiments, the amount of copper metal in the copper salt is inthe range from about 7% to about 12% by weight based on the total weightof the oxychlorination catalyst.

The active salt composition can also comprise an alkali metal salt oroxide. The alkali metal of the alkali metal salts employed in thepresent invention can be selected from the group consisting of sodium,potassium, lithium, rubidium, cesium, and mixtures thereof. The alkalimetal salt can be in the form of a water soluble salt, such as an alkalimetal chloride. However, other alkali metal salts or oxides that wouldconvert to the chloride salts during the oxychlorination process canalso be used, such as the carbonate salts and other halide salts likethe bromide salts. In some embodiments, the alkali metal is potassium,lithium, or cesium. In another embodiment, the alkali metal ispotassium. In one particular embodiment, the alkali metal salt ispotassium chloride. The amount of the alkali metal in the alkali metalsalt can be in the range from about 0.1% to about 8.0% by weight basedon the total weight of the oxychlorination catalyst. In someembodiments, the amount of the alkali metal in the alkali metal salt isin the range from about 0.25% to about 5% by weight based on the totalweight of the oxychlorination catalyst. In other embodiments, the amountof the alkali metal in the alkali metal salt is in the range from about0.5% to about 2.5% by weight based on the total weight of theoxychlorination catalyst.

In some embodiments, the active salt composition comprises a rare earthmetal salt or oxide. The rare earth metal in the rare earth metal saltsused herein can be any of the elements listed as elements 57 through 71in the Periodic Table and the pseudo rare earth elements yttrium andscandium. Non-limiting examples of the rare earth metals includelanthanum, cerium, neodymium, praseodymium, dysprosium, samarium,yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium,thulium, lutetium, and mixtures thereof such as didymium which is amixture of praseodymium and neodymium. The preferred rare earth metalsalts are rare earth metal chlorides. However, other rare earth metalsalts or oxides which would convert into the chloride salts during theoxychlorination process can also be used, e.g., carbonate salts, nitratesalts and other halide salts like bromide salts. The amount of the rareearth metal in the rare earth metal salts can be in the range from about0.1% to about 9% by weight based on the total weight of theoxychlorination catalyst. In some embodiments, the amount of the rareearth metal in the rare earth metal salt is in the range from about 0.5%to about 6% by weight based on the total weight of the oxychlorinationcatalyst. In other embodiments, the amount of the rare earth metal inthe rare earth metal salt is in the range from about 0.5% to about 3% byweight based on the total weight of the oxychlorination catalyst. Inother embodiments, the rare earth metal salt is cerium chloride ordidymium chloride. In some embodiments, the rare earth metal salt is amixture of lanthanum salt and cerium salt where the percentage oflanthanum is greater than the percentage of cerium. The preferred ratioof the percentage of lanthanum to the percentage of cerium is at least2.0. In other embodiments, the rare earth metal salt is a mixture oflanthanum salt and cerium salt where the percentage of cerium is greaterthan the percentage of lanthanum.

In some embodiments, the active salt composition comprises an alkalinemetal salt or oxide. The alkaline metals in the alkaline metal salts canbe magnesium, calcium, strontium, and barium. Preferably, the alkalinemetals are magnesium and barium. The most preferred alkaline metal ismagnesium. The preferred alkaline metal salts are alkaline metalchlorides. However, other alkaline metal salts or oxides which wouldconvert into the chloride salts during the oxychlorination process canalso be used, e.g., carbonate salts, nitrate salts and other halidesalts like bromide salts. The amount of the alkaline metal in thealkaline metal salts can be in the range from about 0.05% to about 6% byweight based on the total weight of the oxychlorination catalyst. Insome embodiments, the amount of the alkaline metal in the alkaline metalsalt is in the range from about 0.25% to about 4% by weight based on thetotal weight of the oxychlorination catalyst. In some embodiments, theamount of the alkaline metal in the rare earth metal salt is in therange from about 0.25% to about 3% by weight based on the total weightof the oxychlorination catalyst.

Optionally, at least one other metal salt or oxide can be present in theactive salt composition in relatively small amounts. Such other metalsalts can be in the form of carbonate, nitrate or halide such aschloride and bromide. Non-limiting examples of such other metals includemain group metals, such as lead, tin, bismuth, gallium and the like, andtransition metals, such as iron, zinc, chromium, nickel, cobalt,scandium, vanadium, titanium, manganese, zirconium, silver, gold,ruthenium, rhodium, palladium and the like. In some embodiments, theamount of each metal in the other metal salts or oxides can be presentin up to about 1 wt % based on the total weight of the oxychlorinationcatalyst. In other embodiments, the amount of each metal in the othermetal salts or oxides can be present in up to about 0.5 wt % based onthe total weight of the oxychlorination catalyst. In furtherembodiments, none of the other metal salts or oxides is present in theactive salt composition.

Any method of preparing oxychlorination catalysts known to a person ofordinary skill in the art can be used to prepare the oxychlorinationcatalyst compositions disclosed herein. Non-limiting examples of suchmethods are described in PCT Patent Application No. WO 81/01284 and U.S.Pat. Nos. 3,488,398; 4,339,620; 4,446,249; 4,740,642; 4,849,393;5,292,703; 5,382,726; 5,600,043; 6,872,684; 6,803,342; 6,777,373;6,759,365; and 6,174,834, and Japanese Patent Publication No. 11-090233.The active salt composition can be added onto the support material byaddition of a solution of the active salt composition in any suitablesolvent such as water, alcohols, dimethyl formamide, dimethyl sulfoxide,ethers, and ketones. The preferred solvent is water. While any metalsalts capable of forming a solution are suitable, the preferred metalsalts are the chloride salts. One non-limiting example of preparing theoxychlorination catalyst includes the step of dissolving in water anactive salt composition comprising one or more metal chlorides such ascopper chloride, alkali metal chlorides, rare earth metal chlorides,alkaline metal chlorides, transition metal chlorides other than copperchloride and combinations thereof The solution can be slowly sprayed onthe support material with continuous mixing (or alternatively thesupport material can be added to the solution with mixing) followed bydrying to remove the solvent contained within the pores or on thesurface of the catalyst. The drying can be performed at any suitabletemperature known to a person of ordinary skill in the art. In someembodiments, the drying temperature is between about 50° C. and about300° C., preferably between about 100° C. and about 200° C.

Alternatively, the active salt composition can be added onto the aluminasupport material by impregnating the support material with an aqueoussolution of an active salt composition comprising one or more watersoluble metal salts, and then drying the wet impregnated supportmaterial at an elevated temperature. The water soluble metal salts canbe chloride, bromide, nitrate or carbonate salts of copper, alkalimetals, rare earth metals, alkaline metals, transition metals other thancopper and combinations thereof. In some embodiments, one or more of themetal salts are calcined on the support material to produce anoxychlorination catalyst. In other embodiments, none of the metal saltsis calcined on the support material. The calcination can be performed atany suitable temperature known to a person of ordinary skill in the art.In some embodiments, the calcination temperature is between about 300°C. and about 700° C., preferably between about 350° C. and about 600° C.

When the active salt composition comprises a copper salt and at leastone active metal salt such as alkali metal salts, rare earth metalsalts, alkaline metal salts, transition metal salts other than a coppersalt and combinations thereof, the copper salt and the active metal saltcan be added, by the procedures described above or any other proceduresknown to a person of ordinary skill in the art, onto the supportmaterial in more than one step and in any order. In some embodiments,the active metal salt is added onto the support material prior to theaddition of the copper salt. In other embodiments, the copper salt isadded onto the support material prior to the addition of the activemetal salt. Optionally, the active metal salt (or the copper salt) isdried or calcined before the addition of the copper salt (or the activemetal salt). In other embodiments, when there are more than one activemetal salt, each of the active metal salts is added onto the supportmaterial individually in a separate step. Optionally, each of the activemetal salts is dried or calcined before the addition of another activemetal salt. In further embodiments, each addition step may add two ormore active metal salts such as copper salts, alkali metal salts, rareearth metal salts, alkaline metal salts, transition metal salts otherthan copper salts and combinations thereof. Based on the disclosureherein, a person of ordinary skill in the art can modify the additionsteps and/or the order of the addition of the active metal salts toobtain an oxychlorination catalyst having desirable properties. Somemulti-step addition or impregnation processes for the preparation of theoxychlorination catalysts are disclosed in PCT Patent Application No. WO81/01284, U.S. Pat. Nos. 4,446,249; 6,872,684; 6,803,342; 6,777,373;6,759,365; and 6,174,834, and Japanese Patent Publication No. 11-090233,all of which are incorporated herein by reference.

In some embodiments, the oxychlorination catalyst can be prepared bywetting the alumina support material, as above described, with anaqueous solution of an active salt composition comprising one or moremetal salts such as copper salts, alkali metal salts, rare earth metalsalts, alkaline metal salts, transition metal salts other than coppersalts and combinations thereof. The wetted alumina support material isthen dried slowly at about 80° C. to 150° C. to remove water. Inparticular embodiments, the metal salts and their amounts are chosen sothat the final oxychlorination catalyst contains from about 2% to about12% by weight of copper, from about 0.2% to about 3.0% by weight of theincorporated alkali metal and from about 0.1% to about 14% by weight ofthe rare earth metal, and from about 0.05% to about 6.0% by weight ofalkaline metal, all of which are based on the total weight of theoxychlorination catalyst. In some embodiments, the total weight ofmetals in the oxychlorination catalysts for fixed-bed catalysis can bebetween about 2.5% and about 35%, between about 3% and about 30%,between about 3% and about 25%, or between about 4% and about 25%, basedon the total weight of the oxychlorination catalyst.

The oxychlorination catalyst can have a surface area between about 25m²/g and about 300 m²/g, as determined by the BET method. In someembodiments, the surface area of the oxychlorination catalyst is betweenabout 50 m²/g and about 250 m²/g. In other embodiments, the surface areaof the oxychlorination catalyst is between about 70 m²/g and about 250m²/g. In further embodiments, the surface area of the oxychlorinationcatalyst is between about 50 m²/g and about 200 m²/g. In certainembodiments, the surface area of the oxychlorination catalyst is betweenabout 70 m²/g and about 150 m²/g.

The oxychlorination catalyst can have an average particle size rangingfrom about 5 to about 300 microns, from about 20 to about 250 microns,from about 20 to about 200 microns, from about 20 to about 150 microns,from about 20 to about 120 microns, from about 30 to about 100 microns,or from about 30 to about 90 microns. The compacted or tamped bulkdensity of the oxychlorination catalyst can vary between about 0.6 andabout 1.6 g/cc, between about 0.7 and about 1.5 g/cc, between about 0.7and about 1.3 g/cc, or between about 0.8 and about 1.3 g/cc.

The oxychlorination catalyst composition comprises a diluent. Ingeneral, a diluent can be used to assist in control of the heat ofreaction and to reduce the levels of oxidation by-products (CO and CO₂)and chlorinated by-product formation. Unexpectedly, as disclosed herein,some oxychlorination catalyst compositions comprising an oxychlorinationcatalyst and a diluent having the proper chemistry and/orcharacteristics can increase the optimal operating temperature of theoxychlorination process while maintaining product selectivity or purity.As disclosed herein, the optimal operating temperature for the catalystin reactors where the majority of the vent gas is recycled back to thereactor is the point where the HCl conversion and the ethyleneselectivity are optimized. For air-based, once-through reactors, theoptimal operating temperature is the point where the HCl conversion andthe ethylene efficiency are optimized. For any given oxychlorinationreactor, catalyst charge and production rate, the optimum operatingtemperature, T_(opt), is that specific reactor control temperaturewhich, when used in conjunction with the optimized HCl/C₂H₄/O₂ reactorfeed ratios, will result in the most economical balance between ethyleneefficiency (or ethylene selectivity for recycle operations), HClconversion (which may impact neutralization costs), HCl efficiency,crude EDC purity (which may impact by-product separation and disposalcosts), and fuel gas value of the vented gases (when remaining ethyleneis used as a fulel gas in a gas incinerator). The most economicalbalance is determined by minimizing the combined cost of the totallosses of chlorine, ethylene, caustic, and crude EDC as liquidby-product for a particular reactor. For any oxychlorination processusing a given reactor and an oxychlorination catalyst without a diluent,the optimum operating temperature of such a process is defined herein asT_(Opt(l)). For any oxychlorination process using a given reactor and anoxychlorination catalyst with a diluent, the optimum operatingtemperature of such a process is defined herein as T_(Opt(2)). In someembodiments, T_(opt(2)) is higher than T_(opt(l)) given that thereactor, quantity of the reactor charge (i.e., either theoxychlorination catalyst or the oxychlorination catalyst with diluent)and production rates (lbs/hr of pure EDC produced) are the same.

The T_(opt(2)) of an oxychlorination process using the oxychlorinationcatalyst composition disclosed herein can be higher than the T_(opt(l))of a corresponding oxychlorination process using the same reactor,reactants, quantity of the reactor charge, production rates andoxychlorination catalyst but without the diluent (e.g., aluminasilicate) disclosed herein. In some embodiments, the T_(opt(2)) of theoxychlorination process using the oxychlorination catalyst compositiondisclosed herein is at least about 1° C., at least about 5° C., at leastabout 10° C., at least about 15° C., at least about 20° C., at leastabout 25° C., or at least about 30° C. higher than the T_(opt(l)) of thecorresponding oxychlorination process without the diluent (e.g., aluminasilicate) disclosed herein using the same reactor, reactants, quantityof the reactor charge, production rates and oxychlorination catalyst.

In general, any catalytically and chemically inert particles that arethermally stable at the optimal operating temperature employed, can beused as a diluent in the oxychlorination catalyst composition disclosedherein. In some embodiments, the optimum operation temperature variesbetween about 170° C. and about 350° C., between about 180° C. and about320° C., between about 190° C. and about 300° C., between about 190° C.and about 250° C., or between about 210° C. and about 250° C.Non-limiting examples of suitable diluents include particles of aluminasilicates, glass beads, silica, ballotini, alumina, graphite, andsilicon carbide. The diluent can be chemically similar to or differentfrom the support material of the oxychlorination catalyst. In someembodiments, the diluent is chemically the same as the support material.In other embodiments, the diluent is chemically different from thesupport material.

In some embodiments, the diluent comprises particles of an aluminasilicate (also known as aluminum silicate or aluminium silicate).Alumina silicates suitable for this invention can include, but are notlimited to, hydrated alumina silicates, hydroxylated alumina silicates,dehydroxylated or anhydrous alumina silicates, and combinations thereofSome non-limiting examples of hydrated alumina silicates includecompounds having the formula Al₂O₃.2SiO₂2H₂O such as kaolin, china clay,kaolinite, dickite, nacrite, kaopectate and porcelain clay, compoundshaving the formula Al₂O₃.2SiO₂.4H₂O such as halloysite, and combinationsthereof Some non-limiting examples of hydroxylated alumina silicates caninclude compounds having the formula Al₂(Si₂O₅)₂(OH)₂ such aspyrophyllite, compounds having the formula Al₂(Si₄O₁₀)₂(OH)₂ such asmontmorillonite, and combinations thereof. Some non-limiting examples ofdehydroxylated or anhydrous alumina silicates include compounds havingthe formula Al₂O₃.SiO₂ such as kyanite, andalusite and sillimanite,compounds having the formula Al₂O₃.2SiO₂ such as metakaolin, compoundshaving the formula 3Al₂O₃.2SiO₂ such as mullite, and combinationsthereof. Each of the alumina silicates may comprise small amounts ofaccessory minerals or impurities. The accessory minerals are mineralsthat may be present in minor amounts in alumina silicates and are notconsidered as essential constituents of the alumina silicates. Anynatural mineral that is not an alumina silicate may be present in thealumina silicates disclosed herein as an accessory mineral. Non-limitingexamples of such accessory minerals include titanium oxide (e.g.,anatase and rutile), feldspar, iron oxides (e.g., Fe₂O₃), sodium salts,potassium salts, calcium oxide, magnesium oxide, mica, montmorilloniteand quartz. In some embodiments, the amount of each of the accessoryminerals or impurities in the alumina silicate may be from about 0.01 wt% to about 10 wt %, from about 0.05 wt % to about 7.5 wt %, or fromabout 0.1 wt % to about 5 wt % of the total weight of the aluminasilicate. In other embodiments, the alumina silicates disclosed hereindo not contain an accessory mineral or impurity.

The alumina silicates can be metal alumina silicates which may containother metal ions in addition to Al³⁺. Some non-limiting examples ofmetal ions include alkali metal ions, alkaline metal ions, transitionmetal ions and combinations thereof. In some embodiments, the metal ionsare Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Be²⁺, Ca²⁺, Mg²⁺, Sr²⁺, Ba²⁺, Co²⁺, Ni²⁺,Cu²⁺, Sn²⁺, Zn²⁺, Mn²⁺, Pb²⁺, Fe²⁺, Fe³⁺ and the like. Some non-limitexamples of metal alumina silicates include magnesium alumina silicate,calcium alumina silicate, sodium alumina silicate, beryllium aluminasilicate, potassium alumina silicate, and the like. In some embodiments,the alumina silicate disclosed herein comprises no metal ion other thanAl³⁺. In other embodiments, the alumina silicate disclosed herein isfree of alkali metal ion, alkaline metal ion, transition metal ion or acombination thereof. In further embodiments, the alumina silicatedisclosed herein is free of alkaline metal ion. In additionalembodiments, the alumina silicate disclosed herein is free of magnesiumion.

The alumina silicates can be classified according to their layerstructures. For example, alumina silicates having a two-layer (i.e.,1:1) structure may include, but are not limited to, kaolin, kyanite,andalusite and sillimanite. Alumina silicates having a three-layer(i.e., 2:1) structure may include, but are not limited to, halloysite,pyrophyllite and montmorillonite. Alumina silicates having a four-layer(i.e., 2:1:1) structure may include, but are not limited to, chlorite.The diluent suitable for this invention can also include other aluminasilicate compounds which have only approximated or undetermined formulaesuch as allophanes and imogolite.

The alumina silicate can include dehydroxylated, dehydrated and/orcalcined products such as metakaolin or mullite obtained bydehydroxylating, dehydrating and/or calcining the hydrated aluminasilicates, such as kaolin, kaolinite, dickite, nacrite and halloysite,at a temperature between about 200° C. and about 1250° C. for about 5minutes to about 7 days. Hereinafter, the terms kaolin, kaolinite,dickite, nacrite and halloysite may include the corresponsding hydratedor partially hydrated forms as well as the above-mentioneddehydroxylated, dehydrated and/or calcined products. In someembodiments, the kaolin, kaolinite, dickite, nacrite or halloysite ishydrated or partially hydrated. In further embodiments, the kaolin,kaolinite, dickite, nacrite or halloysite is totally dehydrated and thusanhydrous. In other embodiments, the alumina silicate disclosed hereinis dehydroxylated, dehydrated or calcined kaolin such as metakaolin(i.e., Al₂O₃.2SiO₂), Si₃Al₄O₁₂, mullite (i.e., 3Al₂O₃.2SiO₂), or acombination thereof. Furthermore, the dehydroxylated, dehydrated orcalcined kaolin may comprise small amounts of accessory minerals asdisclosed above.

The kaoliens disclosed herein can be prepared according to a multi-stepprocess as outlined in Scheme A below. Each step in Scheme A isoptional. For example, if spray drying is used for the drying step andspray drying can be used to control or obtain the desirable particlesize, then the classification step becomes optional and can be omitted.In some embodiments, the calcining temperature in the calcination stepis above about 500° C., about 600° C., about 700° C., about 800° C.,about 900° C., about 1000° C., about 1100° C., about 1200° C., about1300° C., about 1400° C., about 1500° C., about 1600° C., about 1700°C., 1800° C., or about 1900° C. In further embodiments, the calciningtemperature is below about 600° C., about 700° C., about 800° C., about900° C., about 1000° C., about 1100° C., about 1200° C., about 1300° C.,about 1400° C., about 1500° C., about 1600° C., about 1700° C., about1800° C., about 1900° C., or about 2000° C. In other embodiments, thecalcining temperature can be between about 500° C. and about 2000° C.,between about 600° C. and about 1900° C., between about 700° C. andabout 1800° C., between about 800° C. and about 1700° C., between about900° C. and about 1600° C., between about 1000 C and about 1500C,between about 1 100° C. and about 1500° C., between about 1200° C. andabout 1500° C., between about 1100° C. and about 1400° C., between about1200° C. and about 1400° C. or between about 1300° C. and about 1400° C.Further, each step can be carried out in any manner known to personsskilled in the art, such as those described in U.S. Pat. Nos. 6,943,132,6,942,784, 6,942,783, 6,908,603, 6,787,501, 6,696,378, 6,652,642,6,585,822, 6,379,452, 6,346,145, 6,136,086, 6,103,005, 5,997,626,5,968,250, 5,856,397, 5,522,924, 5,395,809, 5,393,340, 5,261,956,5,129,953, 5,112,782, 5,061,461, 5,074,475, 5,028,268, 5,023,220,5,011,534, 5,006,574, 4,678,517, 4,578,118, 4,525,518, 4,427,450, and4,246,039, all of which are incorporated herein by reference in theirentirety. The preparation of kaolins are also described in Kogel et al.,“The Georgia Kaolins: Geology and Utilization,” the Society for MiningMetallurgy & Exploration (2002), which is incorporated herein byreference in its entirety.

In some embodiments, the kaolin disclosed herein can be preparedaccording to following procedure. The kaolin is mined, mixed with waterto form a slurry, and then fractionated into platelets having an averageparticle size from about 0.1 to about 10 microns, from about 0.25 toabout 5 microns, from about 0.5 to about 3 microns, or from about 0.75to about 2 microns. The resulting kaolin slurry then undergoes a waterremoval and spray drying process to form microspheres of the desiredparticle size that are then calcined at a temperature from about 850° C.to about 1300° C., from about 900° C. to about 1200° C. from about 950°C. to about 1100° C. to fuse the platelets having improved attritionresistance.

In other embodiments, the kaolin is in the form of microspheres whichcan be prepared according to the general procedures disclosed in U.S.Pat. Nos. 4,493,902, 6,942,784, 6,943,132 and 7,101,473, all of whichare incorporated herein by reference. A mixture of hydrous kaolin and/ormetakaolin and kaolin that that has been calcined at least substantiallythrough its characteristic exotherm can be mixed with water to form anaqueous slurry. The characteristic exotherm of kaolin has been reportedin the literature such as the article by Zheng et al., “Effect ofProperties of Calcined Microspheres of Kaolin on the Formation ofNaYZeolite,” Bulletin of the Catalysis Society of India, 4, 12-17(2005),which is incorporated herein by reference. The aqueous slurry can bethen spray dried to obtain microspheres comprising a mixture of thehydrous kaolin and/or metakaolin and calcined kaolin. Optionally, amoderate amount of a metal silicate can be added to the aqueous slurrybefore it is spray dried. Some non-limiting examples of suitable metalsilicates include alkali silicates (e.g., sodium silicate, potassiumsilicate), alkaline silicates (e.g., magnesium silicate and calciumsilicate), transitional metal silicates (e.g., titanium silicate andiron silicate) and combinations thereof. In some embodiments, the amountof the metal silicate added to the kaolin is from about 0 wt % to about10 wt %, from about 0.05 wt % to about 8 wt %, or from about 0.1 wt % toabout 6 wt %, based on the total weight of the kaolin. In certainembodiments, the kaolin does not contain a metal silicate.

After spray drying, the microspheres can be calcined directly, oralternatively acid-neutralized. The acid-neutralization processcomprises co-feeding uncalcined, spray dried microspheres and mineralacid to a stirred slurry at controlled pH. The rates of addition ofsolids and acid are adjusted to maintain a pH of about 2 to about 7. Insome embodiments, the pH is maintained at about 2.5 to about 4.5, with atarget pH of about 3. A metal silicate such as sodium silicate can begelled to silica and a soluble sodium salt, which is subsequentlyfiltered and washed free from the microspheres. The silica gel-boundmicrospheres are then calcined.

In either the direct calcination or acid-neutralization process, thecalcination can be carried at a temperature from about 500° C. to about800° C. or about 550° C. to about 650° C. and for a time from 30 minutesto 8 hours in a muffle furnace sufficient to convert any hydrated kaolincomponent of the microspheres to metakaolin, leaving the previouslycalcined kaolin components of the microspheres essentially unchanged.The resulting calcined porous microspheres comprise a mixture ofmetakaolin and kaolin calcined through its characteristic exotherm inwhich both the metakaolin and the previously calcined kaolin are presentin the same microspheres. Alternatively, the porous microspheresobtained previously can be further calcined at a temperature from about1000° C. to about 1300° C. or from about 1000° C. to about 1200° C. andfor a time from 30 minutes to 8 hours in a furnace sufficient to convertpart or all of the metakaolin component of the microspheres to kaolincalcined through its characteristic exotherm to form microspheres inwhich only calcined kaolin are present.

Similarly, the alumina silicate for this invention can include aluminasilicate compounds obtained by dehydroxylating the hydroxylated aluminasilicates, such as pyrophyllite and montmorillonite, at a temperaturebetween about 200° C. and about 1250° C. for about 5 minutes to about 7days. Hereinafter, the terms pyrophyllite and montmorillonite mean thetotally dehydroxylated, partially dehydroxylated, or hydroxylated forms.In some embodiments, the pyrophyllite or montmorillonite ishydroxylated. In other embodiments, the pyrophyllite or montmorilloniteis partially dehydroxylated. In further embodiments, the pyrophyllite ormontmorillonite is totally dehydroxylated.

The amount of the diluent in the oxychlorination catalyst compositionmay be between about 5% and about 95% by weight, based on the totalweight of the oxychlorination catalyst composition. In some embodiments,the amount of the diluent is between 10% and 90% by weight. In otherembodiments, the amount of the diluent is between 20% and 80% by weight.In further embodiments, the amount of the diluent is between 30% and 70%by weight. In additional embodiments, the diluent is an alumina silicatesuch as kaolin in an amount of between about 20% and about 80% by weightbased on the total weight of the oxychlorination catalyst composition.

The diluent can be of any form or shape that is suitable for catalystapplications. In some embodiments, the diluent has an irregular form orshape. In other embodiments, the diluent comprises particles having aregular shape such as sphere, cylinder, disk, bead, drum, oval,platelet, flake, needle, and the like. In further embodiments, thediluent is in the form of microspheres.

The surface area of the diluent can vary between about 0.1 m²/g to about300 m²/g, preferably between about 0.1 to about 100 m²/g, morepreferably between about 0.1 m²/g to about 50 m²/g, most preferablybetween about 0.1 m²/g to less than 25 m²/g, as determined by the BETmethod. In general, when the surface area of the diluent is less than 25m²/g, the diluent may not act as a co-catalyst or promote undesired sidereactions. Not to be bound by theory, it is believed that the diluenthaving a small surface area and/or weaker salt-diluent versussalt-support interaction can avoid the transfer of the active catalystcomponents from the oxychlorination catalyst particles. In someembodiments, the diluents have a surface area less than 25 m²/g. Ingeneral, the low-surface-area diluent can reduce the transfer of theactive catalyst components to the diluent. In other embodiments, thediluents have a surface area greater than 25 m²/g. Optionally, thehigh-surface-area diluent may be inactivated by impregnating withsufficient metal ions, such as alkali metal ions, to reduce to anacceptable level the formation of by-products, such as ethyl chloride,vinyl chloride, 1,1,2-trichloroethane, carbon tetrachloride anddichloroethylene. In a particular embodiment, the diluent is an aluminasilicate such as kaolin having a surface area between about 0.1 m²/g andless than 25 m²/g, preferably between about 1 m²/g and about 20 m²/g,and more preferably between about 3 m²/g and about 16 m²/g, asdetermined by the BET method.

It is desirable that the diluent can be intimately mixed with theoxychlorination catalyst to allow for better fluidization and mixingwithin the reactor. This can be achieved by matching their physicalproperties such as bulk density, average particle size, and particlesize distribution.

The average particle size of the diluent can vary from about 5 to about300 microns, from about 20 to about 250 microns, from about 20 to about200 microns, from about 20 to about 150 microns, from about 20 to about120 microns, from about 30 to about 100 microns, or from about 30 toabout 90 microns. In some embodiments, the average particle size of thediluent is from about 25% to about 200%, from about 50% to about 150%,or from about 75% to about 125% of the average particle size of theoxychlorination catalyst.

The compacted or tamped bulk density of the diluent can vary betweenabout 0.6 and about 1.5 g/cc, between about 0.7 and about 1.4 g/cc,between about 0.7 and about 1.3 g/cc, or between about 0.8 and about 1.2g/cc. In some embodiments, the tamped bulk density of the diluent isabout 25% to about 200% of the tamped bulk density of theoxychlorination catalyst. In other embodiments, the tamped bulk densityof the diluent is about 50% to about 150% of the tamped bulk density ofthe oxychlorination catalyst. In further embodiments, the tamped bulkdensity of the diluent is about 75% to about 125% of the tamped bulkdensity of the oxychlorination catalyst.

In some embodiments, the diluents are particles of alumina silicates. Infurther embodiments, the diluents are calcined kaolin microsphereshaving a surface area between 3 and 16 m²/g and a tamped bulk densitybetween 0.8 and 1.4 g/cc. The physical properties of some suitablecalcined kaolin microspheres are listed in Table 1 below. TABLE 1Particle Size Distribution Data Diluent 1 Diluent 2 Diluent 3 % <16microns 0.79 0.77 0.00 % <22 microns 2.9 2.4 0.85 % <31 microns 8.1 6.13.2 % <44 microns 20 19 9.4 % <88 microns 73 76 49 Attrition (wt %) 65.84.5 3.5 Initial Fines (wt %) 16.7 3.4 5.7 Compacted Bulk 1.04 1.17 1.22Density (g/cc) Surface Area (m²/g) 5.7 6.8 3.2Note:Diluents 1-3 are calcined kaolin microspheres that can be preparedaccording to general preparation procedures as disclosed in Scheme A andparagraphs [56] to [60]; or obtained from Engelhard Corporation, Iselin,NJ.

The average particle size and the particle size distribution data weremeasured with a Honeywell Microtrac X-100 laser particle analyzer by themethod described earlier in this specification. The bulk density can beexpressed in term of compacted bulk density (CBD), sometimes referred toas tamped, tapped, or total bulk density (TBD). The bulk density of thediluent, oxychlorination catalyst or support material can be measured bythe following method. A quantity of approximately 26 g of powder fromeach sample, dried for at least 4 hours at 110° C. and free of anyagglomerates, was introduced into a 50-mL graduated cylinder. Theinitial volume of the packing was observed. Next, the cylinder wasplaced on a Tap-pak Volumeter for a 30 minute run time (about 8770taps). The final or tapped volume of the packing was observed. The CBDor TBD of the sample was calculated by dividing the weight of the powderby the tapped volume of the packing. The attrition properties of thediluents in Table 1 above were measured by the attrition methoddescribed in the Example section below.

The attrition properties of the diluents and catalysts can be measuredby ASTM D5757-00, which is incorporated herein by reference. Theattrition properties of the diluents and catalysts can also be measuredby a similar air-jet method that yields relative results similar tothose produced by the ASTM D5757-00 method. In the air-jet method, anAir-Jet Attrition Instrument can be used. The instrument consists of avertical tubular assembly where a calibrated volume of air (8.8 L/min)can pass through an air cup at the bottom of the assembly. Above the aircup, there is an orifice plate containing three 0.015-inch diameterholes spaced equidistant from the center at 120-degree angles. There isa sample chamber above the orifice plate having a coned interior. Thecone opens upward into a 30-inch long by 1-inch inside diameter sectionof glass pipe. Located at the top of the glass pipe is a separationchamber having an inside diameter significantly larger than the glasspipe. An assembly holding a cellulose extraction thimble resides at thetop of the separation chamber. A weighed volume of catalyst goes intothe sample chamber above the orifice plate. A calibrated volume of airpasses through the orifice openings at sonic speed causing the catalystparticles to collide with one another. The force of the air and theimpacting action of the particles results in an initialdeagglomeration/fines removal and an eventual attrition of theparticles. The airflow transports particles up the glass pipe and intothe separation chamber. Depending on the airflow rate and the generalprinciples as defined by Stokes Law, particles less than the equivalentStokes diameter pass through the chamber and are collected in thethimble. The larger particles fall back into the glass pipe. Thepercentage of material collected in the thimble over time determines theamount of initial fines loss in the sample and the attrition loss. The %of initial fines can be determined by collecting initial fines after 1hour of operation and the % of attrition can be determined by collectingattrition after 5 hours of operation. It is desirable that the % ofinitial fines and the % of attrition of the diluent are respectively inthe same order of magnitude as those of the catalyst. In someembodiments, the % attrition (or the % of initial fines) of the diluentis less than about 10 times the % attrition (or the % of initial fines)of the catalyst. In other embodiments, the % attrition (or the % ofinitial fines) of the diluent is less than about 5 times the % attrition(or the % of initial fines) of the catalyst. In further embodiments, the% attrition (or the % of initial fines) of the diluent is less thanabout 2 times the % attrition (or the % of initial fines) of thecatalyst. In other embodiments, the % attrition (or the % of initialfines) of the diluent is between about 400% and about 10%, between about200% and 25%, or between about 150% and 50% of the % attrition (or the %of initial fines) of the oxychlorination catalyst.

Oxychlorination processes are described in PCT Patent Application No. WO81/01284, U.S. Pat. Nos. 3,488,398; 4,339,620; 4,446,249; 4,740,642;4,849,393; 5,292,703; 5,382,726; 5,600,043; 6,872,684; 6,803,342;6,777,373; 6,759,365; and 6,174,834, and Japanese Patent Publication No.11-090233, all of which are incorporated herein by reference. In someembodiments, the process comprises the step of contacting a hydrocarbonsuch as an unsaturated hydrocarbon (e.g., ethylene), an oxygen sourcesuch as oxygen or oxygen containing gas (e.g., air), and a source ofchlorine such as hydrogen chloride (HCl) with an oxychlorinationcatalyst composition in a reaction zone; and the step of recovering theeffluent from the reaction zone. Some oxychlorination processes includeonce through operations where the unreacted hydrocarbon is vented orremoved, and other oxychlorination processes include recycle operationswherein the unreacted hydrocarbon is recycled back to the reactor oranother unit operation.

In some embodiments, the hydrocarbon is an unsaturated hydrocarbon. Inother embodiments, the hydrocarbon is an olefin having 1-20 carbonatoms. In further embodiments, the olefin includes ethylene and/orpropylene. In a particular embodiment, the hydrocarbon is ethylene andthe oxychlorination product is 1,2 dichloroethane (ethylenedichloride orEDC).

The source of chlorine suitable for the oxychlorination process can beany compound containing chlorine which is capable of transferring itschlorine to the hydrocarbon feed. Non-limiting examples of the source ofchlorine include chlorine gas, hydrogen chloride and any chlorinatedhydrocarbon having one or more reactive chlorine substituents.Non-limiting examples of suitable chlorinated hydrocarbons includecarbon tetrachloride, methylene dichloride and chloroform. Preferably,the source of chlorine is hydrogen chloride.

The source of chlorine may be provided to the oxychlorination process inany amount which is effective in producing the desired oxychlorinationproduct. Typically, the source of chlorine is used in an amount equal tothe stoichiometric amount required by the oxidative chlorinationreaction of interest. For example, in ethylene oxychlorination, fourmoles of hydrogen chloride are employed per mole of oxygen. The hydrogenchloride and oxygen can be employed in amounts which are ideallyselected to facilitate the near complete reaction of both reagents; butgreater and lesser amounts of hydrogen chloride may also be used.

The oxygen source can be any oxygen-containing gas, such as, oxygen gas,air, oxygen enriched air, or a mixture of oxygen gas with an inertcarrier gas. Generally, the feed of reactants to the oxychlorinationreactor is rich in hydrocarbon relative to oxygen (i.e., hydrocarbon isin stochiometric excess).

In some embodiments, the feed comprising the hydrocarbon, source ofchlorine, and source of oxygen can be diluted with an inert carrier gas,which may be any gas that does not substantially interfere with theoxychlorination process. The carrier gas may assist in removing productsand heat from the reactor and in reducing the number of undesirableside-reactions. Non-limiting examples of suitable carrier gas includenitrogen, argon, helium, carbon dioxide, and mixtures thereof Generally,the amount of carrier gas used can range from about 10 to 90 mole %, andpreferably from about 20 to 80 mole %, based on the total moles of thehydrocarbon, source of chlorine, source of oxygen, and inert gasdiluent.

In some embodiments, the feed stream to the oxychlorination processcomprises a mixture of a hydrocarbon such as ethylene, a source ofchlorine such as HCl, an oxygen source, and optionally, a carrier gas.The mixture can be caused to react to form a chlorinated hydrocarbonsuch as EDC under process conditions sufficient to prepare thechlorinated hydrocarbon.

The oxychlorination catalyst compositions are highly efficient catalystsfor the oxychlorination of an unsaturated hydrocarbon such as ethyleneto a chlorinated hydrocarbon such as EDC. The temperature of theoxychlorination process can vary from about 190° C. to about 270° C.,and more preferably from about 210° C. to about 260° C. The reactionpressure can vary from one atmosphere (i.e., 101 kPa) to as high asabout 200 psig (i.e., 1379 kPa). The contact time in the fluid-bed andfixed-bed catalyst systems can vary from about 10 seconds to about 50seconds, and more preferably are from about 15 to 40 seconds. Asdisclosed herein, the contact time is defined as the ratio of reactorvolume taken up by the oxychlorination catalyst composition to thevolumetric flow rate of the feed gases at the reactor controltemperature and reactor top pressure.

In general, the oxychlorination reaction can be run with a mixture of ahydrocarbon, a source of chlorine and an oxygen source in any ratioand/or in any way known to a person of ordinary skill in the art. Askilled artisan can recognize that the optimum feed ratios depend onmany factors such as the design of the reactors, the nature of thehydrocarbon, the nature of the source of chlorine, the nature of theoxygen source, and the like. In some embodiments, the hydrocarbon isethylene, the source of chlorine is HCl and the oxygen source is oxygengas. Some non-limiting examples of feed ratios of ethylene to HCl oroxygen are disclosed in U.S. Pat. Nos. 5,382,726, 6,872,684; 6,803,342;6,777,373; 6,759,365; and 6,174,834, and Japanese Patent Publication No.11-090233, all of which are incorporated herein by reference.

When oxychlorination catalyst compositions disclosed herein are usedunder commercial production conditions in the oxychlorination ofethylene to EDC, the optimum operating temperature can be increased.Higher operating temperature increases the driving force for heatremoval and, therefore, allows for greater reactor productivity. In someembodiments, the optimum operating temperature can be increased by about1 to about 30° C. without sacrificing EDC selectivity, product purity,HCl conversion and catalyst fluidity. Furthermore, all of these catalystperformance benefits are obtained simultaneously without any need tosacrifice one benefit for another.

EXAMPLES

The following examples are presented to exemplify embodiments of theinvention. All numerical values are approximate. When numerical rangesare given, it should be understood that embodiments outside the statedranges may still fall within the scope of the invention. Specificdetails described in each example should not be construed as necessaryfeatures of the invention.

The examples below were developed using a laboratory fluid-bed reactoroperated at atmospheric pressure. However, a person of ordinary skill inthe art can recognize that the oxychlorination catalyst compositionsdisclosed herein and their improved performances can be directlyapplicable to commercial plant reactor operations, on a relative basis,even though the commercial plant reactors typically are operated atelevated temperatures and pressures.

The oxychlorination catalyst compositions are evaluated based upon anumber of criteria including optimal operating temperature, ethyleneconversion, HCl conversion, EDC selectivity, carbon dioxide and carbonmonoxide formation, and triane (1,1,2-trichloroethane) formation. Theethylene conversion or HCl conversion are the amount in mole % ofethylene or HCl consumed respectively in the oxychlorination reactor.The selectivity of a compound, on a C2 (i.e., ethylene) basis, is theyield in mole % of the compound formed in the oxychlorination reactionrelative to the moles of ethylene consumed. The ethylene efficiency isthe product of the ethylene conversion and the EDC selectivity. Forexample, a 99% ethylene conversion and a 95% EDC selectivity wouldresult in a 94% ethylene efficiency.

In the experiments, gaseous reactants, i.e, ethylene, oxygen, andhydrogen chloride were fed to the oxychlorination reactor in molarratios of about 1.0 mole ethylene, about 0.7 mole oxygen, and about 1.9moles hydrogen chloride. In addition to the reactant gases, about 3.0moles of nitrogen was added as an inert carrier gas. For all examplesbelow, the total feed rate of the reactants and nitrogen remainedconstant, and the same oxychlorination reactors and sampling systemswere used during data collection. This allows the comparison of theoxychorination catalyst compositions under identical conditions. As aresult the differences in performance are not due to experimental designbut actual differences in the performance of various oxychlorinationcatalyst compositions. The oxychlorination reactions were conducted attemperatures in the range of about 200° C. to about 260° C. by passingthe reactants through the oxychlorination catalyst bed to produce EDC.The contact times ranged from about 13 to about 17 seconds over thetemperatures tested. The contact time is defined as the ratio of reactorvolume taken up by the oxychlorination catalyst composition to thevolumetric flow rate of the feed gases at the reactor controltemperature and reactor top pressure. The temperatures employed for eachoxychlorination catalyst composition were chosen to include the point ofdesired performance for each oxychlorination catalyst compositiontested. Because different oxychlorination catalyst compositions operatedifferently under different reaction conditions, performance resultsshould be compared under the same conditions. Alternately, a desiredperformance level can be determined, and the conditions necessary toachieve the desired performance level can be compared. For a recycleoperation, the optimal operating temperature corresponds to a rangewhere HCl conversion and ethylene selectivity to EDC are both maximized.Ethylene conversion only becomes important for a once-through processwhere the unreacted feed gases are not recovered. Based on thedisclosure described herein, a person of ordinary skill in the artshould be able to find or modify the process conditions sufficiently toprepare a chlorinated hydrocarbon such as EDC from a hydrocarbon such asethylene.

Diluent 3 was used in Examples 2-4 whereas Diluent 2 was used inExamples 5 and 7-9. The oxychlorination catalyst employed in Examples 1to 5 was a 4-component oxychlorination catalyst according to theinvention claimed in U.S. Pat. No. 5,292,703. The oxychlorinationcatalyst employed in Examples 6 to 9 was a 2-component oxychlorinationcatalyst comprising 3.8 wt % copper and 1.5 wt % magnesium on an aluminasupport. The physical properties of the 4-component and 2-componentoxychlorination catalysts are listed in Table 2 below. The physicalproperties of the oxychlorination catalysts were measured by the samemethods described above for the diluents. TABLE 2 4-Component2-Component Catalyst Catalyst PSD % <88 micron 85 86 % <44 micron 40 30% <31 micron 23 10 % <22 micron 12 3 % <16 micron 6 1 Initial Fines (%)6 2 Attrition (%) 4 4 CBD (g/cc) 1.02 1.02 Surface Area (m²/g) 119 123

Example 1 (Comparative)

In this example the oxychlorination catalyst contained 4.3 wt % copper,1.4 wt % magnesium, 1.2 wt % potassium and 2.3 wt % of a rare earthmixture with a La to Ce ratio of 29 to 1 on a high-surface-area aluminasupport material. The performance test results, at the reactiontemperatures indicated, are shown in Table 3. TABLE 3 Ethylene HCl EDCCO + CO2 1,1,2-Triane Temperature Conversion Conversion SelectivitySelectivity Selectivity ° C. (%) (%) (%) (%) (%) 210 93.31 97.32 98.820.943 0.199 215 94.86 98.77 98.43 1.297 0.211 225 96.46 99.28 96.832.748 0.332 230 97.32 99.14 95.68 3.785 0.401

Example 2

In this example, an oxychlorination catalyst composition comprising 80wt % of substantially the same oxychlorination catalyst as described inExample 1 and 20 wt % of Diluent 3. The oxychlorination catalystcomposition of Example 2 was tested for its catalicic properties and theresults are reported in Table 4. TABLE 4 Ethylene HCl EDC CO + CO21,1,2-Triane Temperature Conversion Conversion Selectivity SelectivitySelectivity ° C. (%) (%) (%) (%) (%) 215 93.53 98.38 99.03 0.757 0.189220 95.12 99.24 98.46 1.261 0.235 230 97.00 99.32 96.76 2.758 0.380 23597.14 99.40 95.43 3.951 0.433

Example 3

In this example an oxychlorination catalyst composition comprising 40 wt% of substantially the same oxychlorination catalyst as described inExample 1 was mixed with 60 wt % of Diluent 3. The oxychlorinationcatalyst composition of Example 3 was tested for its atalitic propertiesand the results are reported in Table 5. TABLE 5 Ethylene HCl EDC CO +CO2 1,1,2-Triane Temperature Conversion Conversion SelectivitySelectivity Selectivity ° C. (%) (%) (%) (%) (%) 225 92.61 97.13 99.450.393 0.156 230 94.32 98.75 98.89 0.785 0.212 235 95.08 99.44 98.351.345 0.264 240 95.56 99.27 97.38 2.170 0.352 245 96.01 98.95 96.343.075 0.448

Example 4

In this example an oxychlorination catalyst composition comprising 20 wt% of substantially the same oxychlorination catalyst as described inExample 1 and 80 wt % of Diluent 3 was prepared. The oxychlorinationcatalyst composition of Example 4 was tested for its catalyticproperties and the results are reported in Table 6. TABLE 6 Ethylene HClEDC CO + CO2 1,1,2-Triane Temperature Conversion Conversion SelectivitySelectivity Selectivity ° C. (%) (%) (%) (%) (%) 240 94.00 98.44 99.010.738 0.233 245 94.71 99.26 98.52 1.118 0.325 250 95.45 99.12 97.711.828 0.379 255 95.75 99.44 97.15 2.300 0.432

Example 5

In this example an oxychlorination catalyst composition comprising 10 wt% of substantially the same oxychlorination catalyst as described inExample 1 and 90 wt % of Diluent 2 was prepared. The oxychlorinationcatalyst composition of Example 5 was tested for its calytic propertiesand the results are reported in Table 7. TABLE 7 Ethylene HCl EDC CO +CO2 1,1,2-Triane Temperature Conversion Conversion SelectivitySelectivity Selectivity ° C. (%) (%) (%) (%) (%) 265 94.82 97.92 96.722.563 0.539 260 94.99 98.23 97.80 1.685 0.387 255 94.13 97.79 98.591.046 0.307 250 92.97 97.17 99.14 0.600 0.216

Example 6 (Comparative)

In this example the catalyst was an oxychlorination catalyst containing3.8 wt % copper and 1.5 wt % magnesium on an alumina support. There wasno diluent. The performance test results, at the reaction temperaturesindicated, are shown in Table 8. TABLE 8 Ethylene HCl EDC CO + CO21,1,2-Triane Temperature Conversion Conversion Selectivity SelectivitySelectivity ° C. (%) (%) (%) (%) (%) 210 93.20 97.84 99.09 0.808 0.093215 95.06 98.38 98.22 1.640 0.129 220 96.18 98.90 97.31 2.482 0.176 22597.35 98.80 95.65 4.034 0.271 230 98.08 98.51 94.15 5.425 0.348

Example 7

In this example an oxychlorination catalyst composition comprising 90 wt% of substantially the same oxychlorination catalyst as described inExample 6 and 10 wt % of Diluent 2 was prepared. The oxychlorinationcatalyst composition of Example 7 was tested for its catalyticproperties and the results are reported in Table 9. TABLE 9 Ethylene HClEDC CO + CO2 1,1,2-Triane Temperature Conversion Conversion SelectivitySelectivity Selectivity ° C. (%) (%) (%) (%) (%) 215 94.22 97.93 98.701.213 0.075 220 95.72 98.67 97.67 2.166 0.148 225 97.18 98.62 96.513.200 0.250 230 98.14 98.64 95.21 4.390 0.342

Example 8

In this example an oxychlorination catalyst composition comprising 50 wt% of substantially the same oxychlorination catalyst as described inExample 6 and 50 wt % of Diluent 2 was prepared. The oxychlorinationcatalyst composition of Example 8 was tested for its catalyticproperties and the results are reported in Table 10. TABLE 10 EthyleneHCl EDC CO + CO2 1,1,2-Triane Temperature Conversion ConversionSelectivity Selectivity Selectivity ° C. (%) (%) (%) (%) (%) 220 92.7896.68 99.24 0.646 0.108 225 94.87 98.35 98.69 1.149 0.155 230 95.8198.71 97.87 1.883 0.234 235 96.89 98.64 96.54 3.141 0.293 240 97.8298.19 95.18 4.397 0.391

Example 9

In this example an oxychlorination catalyst composition comprising 20 wt% of substantially the same oxychlorination catalyst as described inExample 6 and 80 wt % of Diluent 2 was prepared. The oxychlorinationcatalyst composition of Example 9 was tested for its catalyticproperties and the results are reported in Table 11. TABLE 11 EthyleneHCl EDC CO + CO2 1,1,2-Triane Temperature Conversion ConversionSelectivity Selectivity Selectivity ° C. (%) (%) (%) (%) (%) 240 92.4896.30 98.64 1.123 0.236 245 94.26 97.04 97.87 1.819 0.303 250 95.5597.42 96.45 3.124 0.402 255 96.57 97.70 95.39 3.956 0.523

The results of Examples 1 through 4 are graphically represented in FIGS.1-4 wich show that the oxychlorination catalyst compositions of Examples2-4 allow higher reation temperatures without sacrificing otherimportant parameters of the oxychlorination process such as EDCselectivity.

FIG. 1 shows that EDC selectivity is not sacrificed when theoxychlorination catalyst of Comparative Example 1 is combined withDiluent 3 (i.e., a kaolin from Engelhard). Comparative Example 1 havingno diluent has a lower selectivity for the production of EDC fromethylene. Each of Examples 2-4 which have respectively 20 wt %, 60 wt %,and 80 wt % of Diluent 3 displays a higher EDC selectivity thanComparative Example 1. Not only is the selectivity higher, but theselectivity remains high at reaction temperatures that are substantiallyhigher.

FIG. 2 compares the HCl conversion as a function of temperature. Asmentioned above, high HCl conversion is desirable for a variety ofreasons. FIG. 2 shows that diluted catalysts of Examples 2-4 have amaximum HCl conversion of about 99.3-99.5 percent. Yet, these maximumvalues are achieved at higher temperatures than that of ComparativeExample 1. Consequently, Examples 2-4 can be run at higher operatingtemperatures without sacrificing HCl conversion.

As depicted in FIG. 3, the oxychlorination catalyst compositions ofExamples 2-4 show acceptable carbon oxide (i.e., CO and CO₂)selectivity, especially at high reaction temperatures. It is shown hereagain that the oxychlorination catalyst compositions can be used inprocesses running at higher operating temperatures without increasingcarbon oxide selectivity.

FIG. 4 shows that some catalysts described herein can be used inprocesses at increased temperatures without increasing the amount ofby-products such as 1,1,2 trichloroethane (triane). Like the carbonoxide selectivity data, the triane selectivity data indicates that theoxychlorination catalyst compositions can be used at higher operatingtemperatures without increasing the formation of undesirableside-products.

While the invention has been described with respect to a limited numberof embodiments, the specific features of one embodiment should not beattributed to other embodiments of the invention. No single embodimentis representative of all aspects of the invention. In some embodiments,the catalyst compositions may include numerous compounds not mentionedherein. In other embodiments, the compositions do not include, or aresubstantially free of, any compounds not enumerated herein. Someembodiments of the catalyst compositions described herein consist oft orconsist essentially of, the components recited herein. Variations andmodifications from the described embodiments exist. The processesdescribed herein comprise a number of acts or steps. These steps or actsmay be practiced in any sequence or order unless otherwise indicated.Finally, any number disclosed herein should be construed to meanapproximate, regardless of whether the word “about” or “approximately”is used in describing the number. The appended claims intend to coverall those modifications and variations as falling within the scope ofthe invention.

1. An oxychlorination catalyst composition comprising a catalytically effective amount of an oxychlorination catalyst and a diluent comprising particles of an alumina silicate.
 2. The oxychlorination catalyst composition of claim 1, wherein the oxychlorination catalyst composition comprises from about 10 to about 90 percent by weight of the oxychlorination catalyst and from about 90 to about 10 percent by weight of the diluent.
 3. The oxychlorination catalyst composition of claim 1, wherein the surface area of the diluent particles is from about 0.1 m²/g to about 25 m²/g.
 4. The oxychlorination catalyst composition of claim 1, wherein the surface area of the diluent particles is from about 1 m²/g to about 20 m²/g.
 5. The oxychlorination catalyst composition of claim 1, wherein the surface area of the diluent particles is from about 3 m²/g to about 16 m²/g.
 6. The oxychlorination catalyst composition of claim 1, wherein the average particle size of the diluent is between about 25% and about 200% of the average particle size of the oxychlorination catalyst.
 7. The oxychlorination catalyst composition of claim 1, wherein the % attrition of the diluent is between about 50% and about 150% of the % attrition of the oxychlorination catalyst.
 8. The oxychlorination catalyst composition of claim 1, wherein the alumina silicate comprises meta-kaolin, kaolin calcined through its characteristic exotherm, or a combination thereof.
 9. The oxychlorination catalyst composition of claim 8, wherein the alumina silicate is a kaolin calcined through its characteristic exotherm.
 10. The oxychlorination catalyst composition of claim 9, wherein the kaolin are in the form of microspheres.
 11. The oxychlorination catalyst composition of claim 1, wherein the oxychlorination catalyst comprises an active salt composition comprising a copper salt.
 12. The oxychlorination catalyst composition of claim 1, wherein the oxychlorination catalyst comprises a support material having distributed thereon an active salt composition comprising from about 2% to about 12% by weight of copper, from about 0.2% to about 3% by weight of an alkali metal, from about 0.1% to about 14% by weight of a rare earth metal, and from about 0.05% by weight to about 6% by weight of an alkaline metal, all weight percents based upon the total weight of the oxychlorination catalyst.
 13. The oxychlorination catalyst composition of claim 12, wherein the support material and the diluent are different chemically.
 14. The oxychlorination catalyst composition of claim 12, wherein the support material is alumina having a surface area greater than 50 m²/g.
 15. The oxychlorination catalyst composition of claim 1, wherein the oxychlorination catalyst has a surface area from about 25 m²/g to about 300 m²/g.
 16. The oxychlorination catalyst composition of claim 1, wherein the oxychlorination catalyst has a surface area from about 50 m²/g to about 200 m²/g.
 17. The oxychlorination catalyst composition of claim 1, wherein the oxychlorination catalyst has a surface area from about 70 m²/g to about 150 m²/g.
 18. An oxychlorination catalyst composition comprising: (a) a catalytically effective amount of an oxychlorination catalyst having a surface area greater than 25 m²/g where the oxychlorination catalyst comprises a support material having distributed thereon an active salt composition; and (b) a diluent having a surface area between about 0.1 m²/g and about 25 m²/g, wherein the support material and the diluent are different chemically and the average particle size of the catalyst and the diluent is between about 5 and about 300 microns.
 19. The oxychlorination catalyst composition of claim 18, wherein the oxychlorination catalyst comprises an active salt composition comprising a copper salt.
 20. The oxychlorination catalyst composition of claim 18, wherein the active salt composition comprises from about 2% to about 12% by weight of copper, from about 0.2% to about 3% by weight of an alkali metal, from about
 0. 1% to about 14% by weight of a rare earth metal and from about 0.05% by weight to about 6% by weight of an alkaline metal, all weight percents based upon the total weight of the oxychlorination catalyst.
 21. The oxychlorination catalyst composition of claim 18, wherein the diluent is an alumina silicate.
 22. The oxychlorination catalyst composition of claim 18, wherein the average particle size of the diluent is between about 25% and about 200% of the average particle size of the oxychlorination catalyst.
 23. The oxychlorination catalyst composition of claim 22, wherein the tamped bulk density of the diluent is about 25% to about 200% of the tamped bulk density of the oxychlorination catalyst.
 24. The oxychlorination catalyst composition of claim 18, wherein the % attrition of the diluent is between about 50% and about 150% of the % attrition of the oxychlorination catalyst.
 25. A process for the oxychlorination of a hydrocarbon comprising the step of contacting reactants including the hydrocarbon, a source of chlorine, and an oxygen source with an oxychlorination catalyst composition comprising a catalytically effective amount of an oxychlorination catalyst and a diluent comprising particles of an alumina silicate under process conditions to prepare a chlorinated hydrocarbon.
 26. The process of claim 25, wherein the surface area of the diluent particles is from about 0.1 m²/g to about 25 m²/g.
 27. The process of claim 25, wherein the oxychlorination catalyst has a surface area from about 25 m²/g to about 300 m²/g.
 28. The process of claim 25, wherein the average particle size of the diluent is about 25% to about 200% of the average particle size of the oxychlorination catalyst.
 29. The process of claim 25, wherein the alumina silicate is kaolin, nacrite, kyanite, andalusite, sillimanite, pyrophyllite, halloysite, montmorillonite, mullite, allophane, imogolite or a combination thereof.
 30. The process of claim 25, wherein the hydrocarbon is ethylene.
 31. The process of claim 30, wherein the chlorinated hydrocarbon is 1,2-dichloroethane.
 32. The process of claim 25, wherein the source of chlorine is hydrogen chloride and the oxygen source is oxygen gas, air, oxygen enriched air, oxygen gas with an inert carrier gas, or a combination thereof.
 33. The process of claim 25, wherein the reactants are ethylene, hydrogen chloride and the oxygen source, wherein the oxygen source is oxygen gas, air, oxygen enriched air, oxygen gas with an inert carrier gas, or a combination thereof.
 34. The process of claim 25, wherein the process is run at T_(opt(2)), the optimal operating temperature of the process.
 35. The process of claim 34, wherein T_(opt(2)) of the process is at least about 1° C. higher than T_(opt(l)), the optimal operating temperature of a process using the same reactor, reactants, quantity of the reactor charge, production rates and oxychlorination catalyst but without the alumina silicate diluent.
 36. The process of claim 25, wherein the reaction temperature is between about 210° C. and about 260° C.
 37. The process of claim 25, wherein the oxychlorination catalyst comprising a support material having distributed thereon an active salt composition comprising from about 2% to about 12% by weight of copper, from about 0.2% to about 3% by weight of an alkali metal, from about 0.1% to about 14% by weight of a rare earth metal, and from about 0.05% by weight to about 6% by weight of an alkaline metal, all weight percents based upon the total weight of the oxychlorination catalyst.
 38. The process of claim 37, wherein the support material and the diluent are different chemically.
 39. A process for the oxychlorination of a hydrocarbon comprising the step of contacting ethylene, hydrogen chloride, and oxygen gas with an oxychlorination catalyst composition of claim 17 under process conditions to prepare 1,2-dichloroethane.
 40. The process of claim 39, wherein the oxychlorination catalyst comprises an active salt composition comprising a copper salt.
 41. The process of claim 39, wherein the oxychlorination catalyst comprising from about 2% to about 12% by weight of copper, from about 0.2% to about 3% by weight of an alkali metal, from about 0.1% to about 14% by weight of a rare earth metal and from about 0.05% by weight to about 6% by weight of an alkaline metal, all weight percents based upon the total weight of the oxychlorination catalyst.
 42. The process of claim 39, wherein the diluent is an alumina silicate.
 43. The process of claim 39, wherein the average particle size of the diluent is about 25% to about 200% of the average particle size of the oxychlorination catalyst.
 44. The process of claim 39, wherein the compacted bulk density of the diluent is about 25% to about 200% of the compacted bulk density of the oxychlorination catalyst.
 45. The process of claim 39, wherein the % attrition of the diluent is between about 50% and about 150% of the % attrition of the oxychlorination catalyst.
 46. The process of claim 39, wherein the reaction temperature is between about 210° C. and about 260° C.
 47. The process of claim 39, wherein the process is run at an optimal operating temperature.
 48. The process of claim 47, wherein the optimal operating temperature of the process is at least about 1° C. higher than the optimal operating temperature of a process using the same reactants, quantity of the reactor charge, production rates and oxychlorination catalyst but without the diluent.
 49. A process for the oxychlorination of a hydrocarbon comprising the step of contacting reactants including the hydrocarbon, a source of chlorine, and an oxygen source with an oxychlorination catalyst composition comprising a catalytically effective amount of an oxychlorination catalyst and an inert diluent under process conditions to prepare a chlorinated hydrocarbon, wherein the process is run at T_(opt(2)), the optimal operating temperature of the process, which is at least about 1° C. higher than T_(opt(l)), the optimal operating temperature of a process using the same reactor, reactants, quantity of the reactor charge, production rates and oxychlorination catalyst but without the inert diluent. 